JPH0763630B2 - Process for the preparation of coated catalysts based on both bismuth and iron molybdates doped with phosphorus and potassium - Google Patents
Process for the preparation of coated catalysts based on both bismuth and iron molybdates doped with phosphorus and potassiumInfo
- Publication number
- JPH0763630B2 JPH0763630B2 JP3361144A JP36114491A JPH0763630B2 JP H0763630 B2 JPH0763630 B2 JP H0763630B2 JP 3361144 A JP3361144 A JP 3361144A JP 36114491 A JP36114491 A JP 36114491A JP H0763630 B2 JPH0763630 B2 JP H0763630B2
- Authority
- JP
- Japan
- Prior art keywords
- potassium
- phosphorus
- catalyst
- composition
- aqueous solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000003054 catalyst Substances 0.000 title claims description 65
- 238000000034 method Methods 0.000 title claims description 41
- 229910052698 phosphorus Inorganic materials 0.000 title claims description 41
- 229910052700 potassium Inorganic materials 0.000 title claims description 38
- 239000011574 phosphorus Substances 0.000 title claims description 35
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 title claims description 31
- 239000011591 potassium Substances 0.000 title claims description 31
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims description 30
- 230000008569 process Effects 0.000 title claims description 15
- 238000002360 preparation method Methods 0.000 title claims description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title description 12
- 229910052797 bismuth Inorganic materials 0.000 title description 6
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title description 6
- 229910052742 iron Inorganic materials 0.000 title description 6
- 239000000203 mixture Substances 0.000 claims description 43
- 239000002245 particle Substances 0.000 claims description 21
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 claims description 20
- 238000000576 coating method Methods 0.000 claims description 20
- 239000011248 coating agent Substances 0.000 claims description 19
- 239000007864 aqueous solution Substances 0.000 claims description 16
- 150000003112 potassium compounds Chemical class 0.000 claims description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 10
- 239000000853 adhesive Substances 0.000 claims description 8
- 230000001070 adhesive effect Effects 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical class [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 238000010304 firing Methods 0.000 claims description 6
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims description 6
- 235000019796 monopotassium phosphate Nutrition 0.000 claims description 6
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 claims description 6
- -1 phosphorus compound Chemical class 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- 150000003018 phosphorus compounds Chemical class 0.000 claims description 4
- 229940072033 potash Drugs 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 235000015320 potassium carbonate Nutrition 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 229910000396 dipotassium phosphate Inorganic materials 0.000 claims description 2
- 235000019797 dipotassium phosphate Nutrition 0.000 claims description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 2
- 239000011707 mineral Substances 0.000 claims description 2
- 235000010755 mineral Nutrition 0.000 claims description 2
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 claims 2
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 claims 1
- BDRTVPCFKSUHCJ-UHFFFAOYSA-N molecular hydrogen;potassium Chemical compound [K].[H][H] BDRTVPCFKSUHCJ-UHFFFAOYSA-N 0.000 claims 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims 1
- 239000010452 phosphate Substances 0.000 claims 1
- 239000012071 phase Substances 0.000 description 42
- 239000002019 doping agent Substances 0.000 description 21
- 239000000243 solution Substances 0.000 description 19
- 239000010410 layer Substances 0.000 description 17
- 239000004927 clay Substances 0.000 description 16
- 229910052570 clay Inorganic materials 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 13
- 238000000227 grinding Methods 0.000 description 13
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical class N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 10
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 10
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 10
- 238000009826 distribution Methods 0.000 description 9
- 238000007254 oxidation reaction Methods 0.000 description 9
- 239000000725 suspension Substances 0.000 description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 238000001354 calcination Methods 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- 239000002243 precursor Substances 0.000 description 8
- 238000002156 mixing Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 6
- 239000000428 dust Substances 0.000 description 6
- 238000003801 milling Methods 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 5
- 229910021529 ammonia Inorganic materials 0.000 description 5
- 125000004429 atom Chemical group 0.000 description 5
- 229910017052 cobalt Inorganic materials 0.000 description 5
- 239000010941 cobalt Substances 0.000 description 5
- 235000011007 phosphoric acid Nutrition 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 229910052759 nickel Inorganic materials 0.000 description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical group [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- 229920005372 Plexiglas® Polymers 0.000 description 3
- 238000000889 atomisation Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical class [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 229910052785 arsenic Inorganic materials 0.000 description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 2
- 229910052796 boron Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 239000008103 glucose Substances 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 2
- 239000002609 medium Substances 0.000 description 2
- 229910001960 metal nitrate Inorganic materials 0.000 description 2
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 239000004926 polymethyl methacrylate Substances 0.000 description 2
- 239000003361 porogen Substances 0.000 description 2
- 239000004323 potassium nitrate Substances 0.000 description 2
- 235000010333 potassium nitrate Nutrition 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 230000009897 systematic effect Effects 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- 238000009423 ventilation Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 235000002595 Solanum tuberosum Nutrition 0.000 description 1
- 244000061456 Solanum tuberosum Species 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 239000012072 active phase Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- FBXVOTBTGXARNA-UHFFFAOYSA-N bismuth;trinitrate;pentahydrate Chemical compound O.O.O.O.O.[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FBXVOTBTGXARNA-UHFFFAOYSA-N 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 229910052729 chemical element Inorganic materials 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- XAYGUHUYDMLJJV-UHFFFAOYSA-Z decaazanium;dioxido(dioxo)tungsten;hydron;trioxotungsten Chemical compound [H+].[H+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].[NH4+].O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O.[O-][W]([O-])(=O)=O XAYGUHUYDMLJJV-UHFFFAOYSA-Z 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- DKUYEPUUXLQPPX-UHFFFAOYSA-N dibismuth;molybdenum;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Mo].[Mo].[Bi+3].[Bi+3] DKUYEPUUXLQPPX-UHFFFAOYSA-N 0.000 description 1
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 238000003306 harvesting Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000003701 mechanical milling Methods 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000002085 persistent effect Effects 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 125000004437 phosphorous atom Chemical group 0.000 description 1
- 238000001637 plasma atomic emission spectroscopy Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 235000012015 potatoes Nutrition 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052714 tellurium Inorganic materials 0.000 description 1
- PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 238000004846 x-ray emission Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
- B01J27/19—Molybdenum
- B01J27/192—Molybdenum with bismuth
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
- C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
- C07C45/35—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds in propene or isobutene
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
【０００１】本発明の対象は、プロピレンからアクロレ
インを合成するための、燐及びカリウムでドープされた
ビスマス及び鉄の両モリブデン酸塩に基づく被覆された
触媒の製造法である。The object of the present invention is to convert propylene to acrolein.
A process for the preparation of coated catalysts based on both bismuth and iron molybdates doped with phosphorus and potassium for the synthesis of ins .
【０００２】更に詳しくは、本発明は触媒的に活性な中
間組成物を調製し、それを焼成し、続いてその焼成組成
物を粉砕し、外表面が粗になっている不活性な固体支持
体の粒子をその粉砕組成物又はそれを含有する混合物で
被覆し、続いてそのように被覆された粒子を焼成する工
程を含んで成るそのような被覆触媒の製造方法に関す
る。More particularly, the present invention prepares a catalytically active intermediate composition which is calcined, followed by grinding the calcined composition to give an inert solid support having a roughened outer surface. It relates to a process for the preparation of such coated catalysts which comprises the steps of coating the particles of the body with the ground composition or a mixture containing it, followed by calcining the particles so coated.
【０００３】[0003]
【従来の技術】フランス特許第２，０４７，１９９号明
細書において一般式：2. Description of the Related Art In French Patent 2,047,199, the general formula:
【化１】 [Chemical 1]
【０００４】に相当する酸化触媒が考察されている。た
だし、上記の一般式においてCorresponding oxidation catalysts have been considered. However, in the above general formula
【０００５】−Ｌは特に燐を表すことができ、 −Ｍは特にカリウムを表すことができ、 −ａ及びｂは０〜１５であり、かつ和（ａ＋ｂ）は２〜
１５であり、 −ｃは０．５〜７であり、 −ｄは０．１〜４であり、 −ｅは０〜４であり、 −ｆは１２であり、 −ｇは３５〜８５であり、そして −ｈは０．０１〜０．５である。-L can in particular represent phosphorus, -M can in particular represent potassium, -a and b are 0 to 15 and the sum (a + b) is 2 to.
15, -c is 0.5 to 7, -d is 0.1 to 4, -e is 0 to 4, -f is 12, and -g is 35 to 85. , And -h is 0.01 to 0.5.
【０００６】これらの触媒はその元素組成を持つ各種前
駆体から出発する水性媒体中懸濁液を調製し、ペースト
に似たこの懸濁液に（シリカゲルのような）支持体を添
加し、そして加熱、乾固してケーキを得、このケーキを
次に空気の存在下、昇温下において処理することによっ
て製造される。These catalysts prepare a suspension in an aqueous medium starting from various precursors with their elemental composition, add a support (such as silica gel) to this paste-like suspension, and It is produced by heating to dryness to obtain a cake, which is then treated in the presence of air at elevated temperature.
【０００７】これらの触媒は粒子又は錠剤の形で用いら
れる。These catalysts are used in the form of particles or tablets.
【０００８】塊状形態の及び希釈されたこれら触媒は生
産的ではあるが、それらは酸化プロセスを工業的規模で
実施する際に種々の困難をもたらす可能性がある。実
際、固定床においては局所的に昇温される部分が観察さ
れることがあり、これが望ましくない激しい反応を引き
起こす原因となっている。Although these bulk catalysts and diluted catalysts are productive, they can lead to various difficulties in carrying out the oxidation process on an industrial scale. In fact, in the fixed bed, locally heated parts may be observed, which causes an undesired violent reaction.
【０００９】フランス特許第２，２０２，７２９号明細
書には、プロピレンのアクロレインへの酸化に対して、
被覆によって製造される、即ち類似組成の触媒的に活性
な層から形成されるが、その層を金属塩と共に導入され
る支持体により希釈する代わりに直径が少なくとも２０
ミクロンの不活性な支持体の外表面に付着させた触媒を
用いることが有利であることが示される。そのとき固定
床において起こる反応で発生する熱をコントロールする
ことが可能であり、そうすることがより良好である。French Patent 2,202,729 describes the oxidation of propylene to acrolein:
Produced by coating, ie formed of a catalytically active layer of similar composition, but having a diameter of at least 20 instead of being diluted by a support introduced with a metal salt.
It has been shown to be advantageous to use the catalyst deposited on the outer surface of a micron inert support. It is then possible and better to control the heat generated in the reaction taking place in the fixed bed.
【００１０】それにもかかわらず、触媒を形成するこの
特定の方法には触媒の相当部分（そのフランス特許明細
書の唯一の実施例によれば、仕上げ触媒の６６重量％）
を不活性支持体のために残しておくことが求められる。
前者の単に希釈された触媒と比較して活性相のために保
存される部分は減少し、この結果触媒活性に非常に不利
な低下が生ずる。Nevertheless, this particular method of forming the catalyst comprises a considerable part of the catalyst (66% by weight of the finished catalyst, according to the only example of the French patent specification).
Is required to remain for the inert support.
Compared to the former, simply diluted catalyst, the fraction saved for the active phase is reduced, which results in a very detrimental reduction in catalyst activity.
【００１１】このことは、より大きな反応容器に頼って
製造容量及び同一の運転条件を保つようにするか、又は
反応温度を上げて製造容量と反応容器の大きさを維持す
るようにしなければならないときに工業的におのずから
明らかになる。第一のケースでは、主要な不利点は経済
性である。第二のケースでは、２つの不利点が加わる。
即ち、アクロレインの選択性がより低くなり、かつ触媒
活性が時間が経つにつれてより急速に落ちるのである。This means that either a larger reaction vessel must be relied upon to maintain production capacity and identical operating conditions, or the reaction temperature must be increased to maintain production volume and reaction vessel size. Sometimes it becomes industrially self-evident. In the first case, the main disadvantage is economics. In the second case, two disadvantages are added.
That is, the selectivity of acrolein is lower and the catalytic activity drops more rapidly over time.
【００１２】米国特許第４，２９８，７６３号明細書で
は、プロピレンのアクロレインへの酸化反応に対して一
般式：US Pat. No. 4,298,763 describes a general formula for the oxidation reaction of propylene to acrolein:
【化２】 [Chemical 2]
【００１３】に相当する焼成された触媒組成物（活性
相）が推奨されている。ただし、上記の一般式におい
て：A calcined catalyst composition corresponding to (active phase) is recommended. However, in the above general formula:
【００１４】−Ｍ２はニッケル及び／又はコバルトであ
り、ｂは２〜１２の値を有し、 −Ｍ３は特にＫであることができ、ｃは０．０１〜０．
１、好ましくは０．０３〜０．０９の値を有し、 −Ｍ４はＰであり、ｄは０〜１、好ましくは０．０１〜
０．２の値を有し、 −Ｍ５はＩｎ及び／又はＮａであることができ、ｅは０
〜０．５、好ましくは０．０１〜０．２の値を有し、そ
して −ｘは他の諸成分の原子価を飽和するのに要する酸素の
原子数である。-M2 is nickel and / or cobalt, b has a value of 2-12, -M3 can especially be K, and c is 0.01-0.
1, preferably 0.03 to 0.09, -M4 is P, d is 0 to 1, preferably 0.01 to.
Has a value of 0.2, -M5 can be In and / or Na, and e is 0.
Has a value of .about.0.5, preferably 0.01 to 0.2, and --x is the number of oxygen atoms required to saturate the valencies of the other components.
【００１５】この活性相は厚さ１５０〜１５００μｍの
層として支持体に付着される。支持体は直径１００μｍ
以上、表面積１５ｍ２／ｇ未満の中心コアでもある。This active phase is applied to the support as a layer with a thickness of 150 to 1500 μm. Support has a diameter of 100 μm
As described above, it is also a central core having a surface area of less than 15 m 2 / g.
【００１６】焼成された、粒子寸法が０．１〜３００μ
ｍの粉末状触媒物質の層の付着は湿った媒体中で行われ
る。この場合、支持体粒子は激しく撹拌され、その上制
御された操作条件が特定される。Calcinated, particle size 0.1-300μ
The deposition of a layer of m of powdered catalytic material is carried out in a moist medium. In this case, the support particles are vigorously agitated and additionally controlled operating conditions are specified.
【００１７】中心の支持コアを被覆する層は支持体重量
の少なくとも５０％、即ち仕上げ触媒の少なくとも３３
重量％に相当し、そして支持体重量に対して多くても２
５０％、即ち仕上げ触媒に対して多くても７１．４％で
ある。The layer covering the central support core is at least 50% by weight of the support, ie at least 33 of the finished catalyst.
Equivalent to weight% and at most 2 relative to the weight of the support
50%, ie at most 71.4% with respect to the finished catalyst.
【００１８】この被覆触媒はオレフィンの酸化反応にお
いて用いられる前に乾燥され、そして必要ならば４００
〜７００℃の温度で焼成される。The coated catalyst is dried before being used in the olefin oxidation reaction, and if necessary 400
It is fired at a temperature of ~ 700 ° C.
【００１９】この米国特許明細書の教示から、当該支持
体を被覆する触媒組成物の成分はその全てが組成物の焼
成及び粉砕の前に存在することは明らかである。From the teaching of this US patent it is clear that all of the components of the catalyst composition coating the support are present prior to calcination and grinding of the composition.
【００２０】この米国特許明細書の実施例１にはモリブ
デン原子１２個当たり燐原子を０．０６個及びカリウム
原子を０．０６個含有する組成物が開示される。ここ
で、後者の２元素はＫＯＨ及び燐酸の形で水性溶液に導
入され、その後沈澱及びその懸濁液全体の微粒化が行わ
れる。微粒化された前駆体は次にもう１つの水性ポタッ
シュ（ｐｏｔａｓｈ）溶液と再混合され、その後押し出
され、次いで乾燥及び焼成される。Example 1 of this US patent discloses a composition containing 0.06 phosphorus atoms and 0.06 potassium atoms per 12 molybdenum atoms. Here, the latter two elements are introduced into the aqueous solution in the form of KOH and phosphoric acid, followed by precipitation and atomization of the entire suspension. The atomized precursor is then remixed with another aqueous potash solution, then extruded, then dried and calcined.
【００２１】これらのドーパントは従って活性相の前駆
体に導入され、その後活性相が焼成中に生成する。この
導入法には次の主たる不利点がある：These dopants are thus introduced into the precursor of the active phase, after which the active phase is produced during firing. This introduction method has the following major disadvantages:
【００２２】−２回の秤量操作を必要とし、従って誤差
の入る危険が２回となる２つの異なる道筋でポタッシュ
を導入することが必要であるので、複雑さが一層大き
い；Greater complexity, since it is necessary to introduce the potatoes in two different ways, which requires two weighing operations and therefore two risk of error.
【００２３】−燐ドーパントの有利な役割が触媒反応が
起こる活性相粒子の表面で果たされるとしても、前駆体
粒子内部でのそれらドーパントの損失が著しい；及び −微粒化後に混合によって添加されるカリウムの顕微鏡
的分布のコントロール性が乏しい。微粒化によって単に
乾燥されたこのような前駆体には、一般に、カリウムが
全て全固体粒子上に均一に分布するのを妨害するのに十
分な濃度のカチオンの吸着部位がある。粒子スケール上
の燐対カリウムの原子比のコントロール性が乏しいと、
その原子比の値が仕上げ触媒の活性度に著しく影響を及
ぼすものとなる。The loss of these dopants inside the precursor particles is significant, even if the advantageous role of phosphorus dopants is fulfilled at the surface of the active phase particles where the catalysis takes place; and-potassium added by mixing after atomization. The controllability of the microscopic distribution of is poor. Such precursors, simply dried by atomization, generally have a sufficient concentration of cation adsorption sites to prevent the potassium from being evenly distributed over all the solid particles. Poor control of the atomic ratio of phosphorus to potassium on the particle scale,
The value of the atomic ratio significantly affects the activity of the finished catalyst.
【００２４】米国特許第４，６２１，０７２号明細書は
特に、粗表面を有する粒子寸法が０．５〜６ｍｍである
不活性な支持体を含み、触媒的に活性な物質の層がその
支持体を被覆し、かつその支持体に固定されている，耐
磨耗性の被覆触媒の製造法に関する。US Pat. No. 4,621,072 particularly comprises an inert support having a rough surface and a particle size of 0.5 to 6 mm, in which a layer of catalytically active material is used. The present invention relates to a method for producing a wear-resistant coated catalyst which coats a body and is fixed to its support.
【００２５】この米国特許明細書では、触媒の固定床反
応容器における工業的規模での使用に対して十分な機械
的性質を有する被覆層を得るために、被覆触媒を製造す
るときに遭遇する種々の困難が詳細に説明されている。
この米国特許明細書では次いで、これらの不利点を克服
する種々の対策が提案され、そして、中でも、バインダ
ー及び、必要ならば、ポロジェニック剤（ｐｏｒｏｇｅ
ｎｉｃ ａｇｅｎｔ）も含有する触媒的に活性な物質の
前駆体の懸濁液を使用することが推奨されている。この
場合も、その前駆体は最終的な特定の焼成熱処理による
触媒的に活性な物質の形成に必要な全成分を含有してい
る。In this US patent the various catalysts encountered when producing coated catalysts in order to obtain a coating layer with sufficient mechanical properties for industrial scale use of the catalyst in fixed bed reactors. The difficulties are explained in detail.
The US patent specification then proposes various measures to overcome these disadvantages, and among others, a binder and, if necessary, a porogenic agent.
It is recommended to use a suspension of the precursor of the catalytically active substance, which also contains a nic agent). Again, the precursor contains all of the components necessary for the final specific calcining heat treatment to form the catalytically active material.
【００２６】この被覆法で、仕上げ触媒中の活性相が有
意の重量割合であるにもかかわらず、良好な機械的耐性
が得られるようにするためには特定の注意を払わなけれ
ばならないだろう。With this coating method, particular care will have to be taken in order to obtain good mechanical resistance despite the significant weight proportion of active phase in the finished catalyst. .
【００２７】この場合も、ドーパントの燐及びカリウム
の可能な導入法には既に述べた不利点がある。In this case too, the possible introduction of the dopants phosphorus and potassium has the disadvantages already mentioned.
【００２８】加えて、既に述べた全ての方法におけるご
とく、この方法においても触媒的に活性な相の製造に用
いられる適当な水溶性塩は金属硝酸塩、モリブデン酸ア
ンモニウム、硝酸カリウム及び燐酸である。従って、こ
の製造中に硝酸アンモニウムが形成され、これは後続の
焼成中に約２３０℃において熱分解する。In addition, as in all the processes already mentioned, suitable water-soluble salts which are also used in this process for preparing the catalytically active phase are metal nitrates, ammonium molybdate, potassium nitrate and phosphoric acid. Thus during this production ammonium nitrate is formed which pyrolyzes at about 230 ° C. during the subsequent calcination.
【００２９】硝酸アンモニウムのこの熱分解が実施上重
大な問題をもたらすことは明らかである。実際、硝酸ア
ンモニウムは爆発性の化合物であって、この点で工業的
規模で取り扱うのは危険であることは当業者のよく知る
ところである。It is clear that this thermal decomposition of ammonium nitrate poses serious problems in practice. Indeed, it is well known to those skilled in the art that ammonium nitrate is an explosive compound and in this respect handling on an industrial scale is dangerous.
【００３０】フランス特許第２，４８１，１４６号が更
に知られており、この明細書にはモリブデン及び／又は
タングステンの酸化物と他の金属の酸化物とに基づく触
媒の製造法が記載される。この方法は硝酸アンモニウム
の熱分解を回避できるようにする方法である。この方法
の特徴は第一段階においてアンモニウム、モリブデン及
びタングステンの各塩を含有する第一水性溶液に金属塩
を含有する第二溶液を加え、第二段階においてアンモニ
アを得られた混合物に出発第一水性溶液のｐＨより大き
いｐＨが得られるまで加え、次いで得られた懸濁液を濾
過してケーキを得、次にそのケーキを焼成して活性相を
作る点にある。この方法によれば、一方では母液に可溶
性の硝酸アンモニウムが、他方ではフイルターケーキの
形の活性相前駆体が容易に分離できるようになる。この
方法は前に述べた特許明細書に記載されるビスマスと鉄
の両モリブデン酸塩に基づく処方物に適用することがで
きる。ただし、当業者がよく知るように、その使用条件
下では硝酸カリウム及び燐酸が可溶であるので、母液に
これらの元素が吸収されてしまう。従って、この方法で
は特定量の燐とカリウムを活性相にコントロールされた
様式で導入することは可能でない。French Patent 2,481,146 is further known, which describes a process for preparing catalysts based on oxides of molybdenum and / or tungsten and oxides of other metals. . This method is a method that makes it possible to avoid thermal decomposition of ammonium nitrate. This method is characterized in that in the first step, a second aqueous solution containing metal salts is added to a first aqueous solution containing salts of ammonium, molybdenum and tungsten, and in a second step, ammonia is obtained in the mixture obtained by starting first. The point is to add until a pH greater than that of the aqueous solution is obtained, then filter the resulting suspension to obtain a cake, then bake the cake to make the active phase. According to this method, ammonium nitrate soluble in the mother liquor on the one hand and the active phase precursor in the form of a filter cake on the other hand can be easily separated. This method can be applied to the bismuth and iron molybdate-based formulations described in the aforementioned patent specifications. However, as well known to those skilled in the art, potassium nitrate and phosphoric acid are soluble under the conditions of use, so that these elements are absorbed in the mother liquor. Therefore, it is not possible with this method to introduce specific amounts of phosphorus and potassium into the active phase in a controlled manner.
【００３１】[0031]
【発明が解決しようとする課題】従って、気付かれるだ
ろうように、従来法の豊富な教示にもかかわらず、特に
ビスマスと鉄の両モリブデン酸塩に基づく、及び、必要
によっては、その他の元素に基づく、そして燐とカリウ
ムを含有する被覆された触媒組成物であって、前記の色
々な危険を無くし、実施が比較的簡単であり、そしてド
ーパントの触媒的に活性な層中への適当な分布、最終触
媒組成物の正確なコントロール及び満足できる再現性を
確実に達成できる被覆触媒組成物の製造法の必要が残っ
ている。また、そのような方法を満足できる機械的耐性
を有し、ドーパントである燐及びカリウムを可能な最少
量で導入することができる被覆触媒の製造に利用できる
ようにすることも極めて望ましい。Therefore, as will be noticed, in spite of the abundant teaching of the prior art, it is based in particular on both bismuth and iron molybdates and, if desired, on other elements. A coated catalyst composition based on, and containing phosphorus and potassium, which eliminates the various risks mentioned above, is relatively simple to implement, and is suitable for inclusion in a catalytically active layer of dopant. There remains a need for a method of making a coated catalyst composition that can ensure distribution, precise control of the final catalyst composition, and satisfactory reproducibility. It would also be highly desirable to have such a method available for the production of coated catalysts having satisfactory mechanical resistance and capable of incorporating the dopants phosphorus and potassium in the smallest possible amounts.
【００３２】[0032]
【課題を解決するための手段】本発明の主題は、従っ
て、触媒的に活性な中間組成物を調製し、それを焼成
し、続いてその焼成組成物を粉砕し、外表面が粗になっ
ている不活性な固体支持体の粒子をその粉砕組成物又は
それを含有する混合物により被覆し、続いてそのように
被覆された粒子を焼成する工程を含んで成る、特に燐及
びカリウムでドープされたビスマスタイプ及び鉄タイプ
の両モリブデン酸塩の被覆された触媒の製造法におい
て、（ａ）カリウム及び燐を含まない触媒的に活性な中
間組成物を調製し、そして（ｂ）カリウム及び燐の導入
を被覆段階中に実施することを特徴とする前記方法であ
る。The subject of the present invention is therefore to prepare a catalytically active intermediate composition, calcining it, followed by grinding the calcined composition to roughen the outer surface. Comprising particles of an inert solid support being coated with the milling composition or a mixture containing it, followed by calcining the particles so coated, especially doped with phosphorus and potassium. In a process for the preparation of both bismuth-type and iron-type molybdate coated catalysts, (a) preparing a catalytically active intermediate composition free of potassium and phosphorus, and (b) adding potassium and phosphorus. Said method, characterized in that the introduction is carried out during the coating step.
【００３３】本発明による方法は、従って、カリウム及
び燐を含まない触媒的に活性な中間組成物の調製を含
む。The process according to the invention therefore comprises the preparation of a catalytically active intermediate composition which is free of potassium and phosphorus.
【００３４】当該中間組成物（ドープされていない、即
ち中間の活性相）の正確な性質は特別重大なものではな
い。この組成物がプロピレンをアクロレインに酸化する
ための高性能触媒の製造に従来用いられた化学元素を含
有しているからである。本発明の方法に関係のある状況
ではこの中間組成物はモリブデン酸ビスマス及び鉄から
本質的に形成され、次式：The exact nature of the intermediate composition (undoped, ie intermediate active phase) is not of particular importance. This is because this composition contains the chemical elements conventionally used in the production of high performance catalysts for the oxidation of propylene to acrolein. In the context of the process of the invention, this intermediate composition is essentially formed from bismuth molybdate and iron and has the formula:
【化３】 [Chemical 3]
【００３５】で表すことができる。ただし、上記の式に
おいてIt can be represented by However, in the above formula
【００３６】−Ａはコバルト、ニッケル、マンガン、亜
鉛、マグネシウム、鉛、クロム、バナジウム、セリウム
及びランタンより成る群から選択される少なくとも１種
の金属を表し、 −Ｆは砒素、インジウム、アンチモン、錫、テルル、セ
レン、珪素、硫黄及び硼素より成る群から選択される少
なくとも１種の元素を表し、 −Ｇはアルカリ土類金属、ニオブ及びタリウムより成る
群から選択される少なくとも１種の元素を表し、 −ａは金属Ａの各々に配された指数の和を表し、かつそ
れは０〜１２であり、 −ｂ及びｃは各々０〜１２であって、それらの和は１２
に等しく、 −ｄは０．２〜６、好ましくは０．５〜３であり、 −ｅは０．２〜６、好ましくは０．５〜３であり、 −ｆは金属Ｆの各々に配された指数の和を表し、かつそ
れは０〜４、好ましくは０．５〜２であり、そして −ｇは金属Ｇの各々に配された指数の和を表し、かつそ
れは０〜４、好ましくは０．５〜２である。-A represents at least one metal selected from the group consisting of cobalt, nickel, manganese, zinc, magnesium, lead, chromium, vanadium, cerium and lanthanum, and -F represents arsenic, indium, antimony, tin. , At least one element selected from the group consisting of tellurium, selenium, silicon, sulfur and boron, -G represents at least one element selected from the group consisting of alkaline earth metals, niobium and thallium. , -A represents the sum of the indices assigned to each of the metals A, and it is 0-12, -b and c are each 0-12, and their sum is 12
, -D is 0.2 to 6, preferably 0.5 to 3, -e is 0.2 to 6, preferably 0.5 to 3, and -f is assigned to each metal F. Represents the sum of the indices assigned to each of the metals G, and it is 0-4, preferably 0.5-2, and -g represents the sum of the indices assigned to each of the metals G, and it is 0-4, preferably It is 0.5-2.
【００３７】この中間組成物（非ドープ触媒相）は自体
公知の方法に従って、特にフランス特許第２，４８１，
１４６号及び同第２，４９１，７７８号明細書に記載さ
れる沈澱法に従って調製される。第一の引用特許に記載
される方法は次のように要約することができる。即ち、This intermediate composition (undoped catalyst phase) is prepared according to methods known per se, in particular French patent 2,481,
It is prepared according to the precipitation method described in US Pat. Nos. 146 and 2,491,778. The method described in the first cited patent can be summarized as follows. That is,
【００３８】第一段階において、群Ａの金属並びに鉄及
びビスマスの可溶性の塩、即ち硝酸塩又は塩化物の溶液
をビスマスの加水分解を回避するために硝酸で酸性にさ
れた第一溶液中で調製する。この第一溶液のｐＨは１〜
２である。第二段階で、この第一溶液をヘプクモリブデ
ン酸アンモニウム及び、場合によっては、パラタングス
テン酸アンモニウム、並びに元素Ｆ及びＧの可溶性化合
物の溶液に激しく撹拌しながら導入する。ここで第一の
沈澱が起こる。第三段階で、アンモニアを、なお撹拌し
ながらｐＨが約６〜約９に増加するまで加える。かくし
て、沈澱が完結する。この時点でドーパントのＦ及びＧ
を不溶性化合物の形で添加することが可能である。In a first step, a solution of a Group A metal and a soluble salt of iron and bismuth, ie a nitrate or chloride, is prepared in a first solution acidified with nitric acid to avoid hydrolysis of bismuth. To do. The pH of this first solution is 1 to
It is 2. In the second stage, this first solution is introduced with vigorous stirring into a solution of ammonium hepcumolybdate and optionally ammonium paratungstate and soluble compounds of the elements F and G. Here the first precipitation occurs. In the third stage, ammonia is added with still stirring until the pH increases to about 6 to about 9. Thus the precipitation is complete. At this point the dopants F and G
Can be added in the form of an insoluble compound.
【００３９】アンモニア溶液は５０〜約２５０ｇのアン
モニアを含有し、混合物のリットル当たりアンモニア約
２０〜約２００ｇ／時の速度で添加される。その後、化
合物類の沈澱を完結させるために懸濁液を３０〜１００
℃の温度に約１時間加熱するのが好ましい。次に、懸濁
液を濾過する。The ammonia solution contains 50 to about 250 g of ammonia and is added at a rate of about 20 to about 200 g / hr of ammonia per liter of mixture. The suspension is then added to 30-100 to complete the precipitation of the compounds.
It is preferred to heat to a temperature of ° C for about 1 hour. Then the suspension is filtered.
【００４０】次に、フィルターケーキを６ｃｍ未満の厚
さで広げ、次いでオーブンに入れる。焼成はその温度を
１００〜２００℃／時の速度で漸進的に上げることによ
って行う。温度を次に４００〜４６０℃の安定な値に６
時間保ち、次いで数時間かけて冷却を行う。The filter cake is then spread to a thickness of less than 6 cm and then placed in an oven. Firing is performed by gradually increasing the temperature at a rate of 100 to 200 ° C./hour. The temperature is then set to a stable value of 400-460 ° C.
Hold for hours, then cool over several hours.
【００４１】こうして得られた中間組成物を次に公知の
手段でその粒子寸法が４００マイクロメーターを越えな
いように粉砕する。The intermediate composition thus obtained is then ground by known means so that its particle size does not exceed 400 micrometers.
【００４２】本発明による方法は固体支持体の粒子を被
覆する工程を含む。The method according to the invention comprises the step of coating the particles of the solid support.
【００４３】本発明による方法が関係する状況において
用いることができる支持体は直径０．５〜６ｍｍの固体
球体の形で存在するが、当業者であればその正確な値は
酸化反応容器に容認される仕込み損失の関数として選択
することができるだろう。この支持体の化学的性質はそ
れが諸試薬に対して化学的に不活性である限り重要では
ない。シリカ、アルミナ、シリカ−アルミナ、焼結クレ
ー、カーボランダム、マグネシア又は珪酸マグネシウム
が有利に用いられる。The supports which can be used in the context of the process according to the invention are present in the form of solid spheres with a diameter of 0.5 to 6 mm, the exact value of which is known to the person skilled in the art for the oxidation reactor. You will be able to choose as a function of the stockpiling loss. The chemistry of this support is not critical so long as it is chemically inert to the reagents. Silica, alumina, silica-alumina, sintered clay, carborundum, magnesia or magnesium silicate are preferably used.
【００４４】支持体表面は球体の平均直径に対するでこ
ぼこの高さによって定義することができる粗さを有して
いるのが望ましい。この比率は０．１〜０．２であるの
が好ましい。The support surface preferably has a roughness which can be defined by the height of the irregularities relative to the average diameter of the spheres. This ratio is preferably 0.1 to 0.2.
【００４５】被覆は支持体の球体を活性相の外層で次第
に包囲して行く操作である。この操作は、粉砕された活
性相の粒子を前記のように導入する手段と接着剤の水性
溶液を導入する手段とを備えた回転式コーターにそれら
球体を導入することによって自体公知のやり方で実施さ
れる。本発明方法の本質的特性によれば、カリウム及び
燐の導入はこの被覆段階中に行われる。Coating is an operation in which the spheres of the support are gradually surrounded by an outer layer of active phase. This operation is carried out in a manner known per se by introducing the spheres into a rotary coater equipped with means for introducing the particles of ground active phase as described above and means for introducing an aqueous solution of adhesive. To be done. According to the essential characteristics of the process according to the invention, the introduction of potassium and phosphorus takes place during this coating step.
【００４６】１つの実施法によれば、コーターには少な
くとも１種のカリウム化合物と少なくとも１種の燐化合
物とが微粉砕された粉末の形で、同時に中間触媒組成物
及び接着剤溶液と共に導入される。According to one embodiment, the coater is introduced with at least one potassium compound and at least one phosphorus compound in the form of a finely divided powder, simultaneously with the intermediate catalyst composition and the adhesive solution. It
【００４７】有利な実施法によれば、この導入は少なく
とも１種のカリウム化合物と少なくとも１種の燐化合物
との水性溶液を導入することによって当該コーター中で
行われる。１種又は２種以上の燐化合物及び１種又は２
種以上のカリウム化合物の水中熔解度は２５℃において
測定して１０ｇ／Ｌ（リットル）より大であるのが好ま
しい。According to a preferred practice, this introduction is carried out in the coater by introducing an aqueous solution of at least one potassium compound and at least one phosphorus compound. One or more phosphorus compounds and one or two
The solubility of one or more potassium compounds in water is preferably greater than 10 g / L (liter) as measured at 25 ° C.
【００４８】カリウム化合物及び燐化合物は被覆溶液の
他の成分、特に接着剤及び、もし適用できるならば、ポ
ロゲン（ｐｏｒｏｇｅｎ）に対して不活性なものの中か
ら選択されるべきである。これらの化合物は更に、後続
の焼成中に熱分解されることができるべきであるが、接
着剤及びポロゲンを破壊すべきではない。実際には、選
択された燐化合物及びカリウム化合物の添加は水性溶液
をｐＨ値３〜１１にもたらすべきである。The potassium compound and the phosphorus compound should be chosen among the other components of the coating solution, in particular the adhesive and, if applicable, those which are inert to the porogen. These compounds should also be capable of being pyrolyzed during subsequent firing, but should not destroy the adhesive and porogen. In practice, the addition of the selected phosphorus and potassium compounds should bring the aqueous solution to a pH value of 3-11.
【００４９】ポタッシュがカリウムの適した化合物であ
り；鉱物質又は有機の燐酸塩及び燐酸が燐の適した化合
物の例である。Potash is a suitable compound of potassium; mineral or organic phosphates and phosphoric acids are examples of suitable compounds of phosphorus.
【００５０】本発明の好ましい変法によれば、これら２
種の元素は燐酸二水素カリウム又は燐酸−水素カリウム
等の共通の化合物に頼ることによって同時に導入され
る。必要であるだろう元素の各々の残りはポタッシュか
燐酸のどちらかを添加することによって与えることが可
能である。一般式：According to a preferred variant of the invention, these two
The seed elements are introduced simultaneously by relying on a common compound such as potassium dihydrogen phosphate or potassium hydrogen phosphate. The balance of each of the elements that may be needed can be provided by adding either Potash or phosphoric acid. General formula:
【化４】 [Chemical 4]
【００５１】（式中、ｘは０〜３である。）(In the formula, x is 0 to 3.)
【００５２】に相当するヘテロ酸の塩も適当な燐化合物
の例として必要ならば挙げることができ、これらもカリ
ウムに関して共通である。Salts of the hetero acids corresponding to can also be mentioned if necessary as examples of suitable phosphorus compounds, which are also common for potassium.
【００５３】本発明による方法の有利な変法によれば、
燐及びカリウムの両化合物は接着剤の水性溶液に導入さ
れる。According to an advantageous variant of the method according to the invention,
Both phosphorus and potassium compounds are introduced into an aqueous solution of adhesive.
【００５４】被覆操作はダストが注意深く除去された８
０〜１６０ｋｇの粗面の支持体球体が入っている、１０
〜２０回転／分で回転している回転式コーターの中で行
われる。次いで、シュートで粉砕中間触媒組成物３０〜
５０ｋｇ／時が、また加圧下のポンプで接着剤と燐及び
カリウムの両化合物の水性溶液８〜１０Ｌ／時が同時に
導入される。好ましい変法においては、球体はドーパン
トを含有していない接着剤の水性溶液で前以て湿化され
ている。The coating operation was carried out by carefully removing dust.
Includes 0-160 kg rough support spheres, 10
Done in a rotary coater rotating at ~ 20 rpm. Then, with a chute, the intermediate catalyst composition 30-
50 kg / hour and 8 to 10 L / hour of an adhesive and an aqueous solution of both phosphorus and potassium compounds are simultaneously introduced by a pump under pressure. In a preferred variant, the spheres are pre-moistened with an aqueous solution of adhesive containing no dopant.
【００５５】操作は全被覆溶液が、次いで全中間活性相
が使用されるまで続けられる。回転は数分間継続して活
性相の層が球体に真に圧縮されるようにする。それらを
次いで８０〜１５０℃の熱風で１０〜３０分間乾燥し、
そしてオーブンに導入する。これらオーブンの温度を３
〜１５時間かけて４５０〜５００℃の安定な値まで直線
的に上げる。次に、３〜１０時間かけて冷却する。好ま
しい変法においては、第二の焼成が第一の焼成における
と同じ温度変化の条件下で連続的に行われる。もう１つ
の好ましい変化法においては、安定な焼成温度は４８０
℃である。The operation is continued until the entire coating solution is used and then the entire intermediate active phase is used. The rotation is continued for a few minutes so that the layer of active phase is truly compressed into the sphere. They are then dried with hot air at 80-150 ° C for 10-30 minutes,
Then put it in the oven. Set the temperature of these ovens to 3
Increase linearly to a stable value of 450-500 ° C over ~ 15 hours. Next, it cools over 3 to 10 hours. In a preferred variant, the second calcination is carried out continuously under the same temperature change conditions as in the first calcination. In another preferred variation, the stable firing temperature is 480
℃.
【００５６】導入されたドーパント成分は、ほぼ実質的
に完全にドーパントとして配合されかつ被覆中の各フラ
クション（各位置）における組成がほぼ等しいという意
味で再現性がある。即ち、それは被覆中に用いられる水
性溶液に最終触媒組成物に所望とされる化学量論比を得
るのに理論的に必要な燐及びカリウムの両化合物の量に
近い量（±５％以内）だけ導入することが可能である。The introduced dopant component is substantially and almost completely compounded as a dopant and in each fraction in the coating.
Meaning that the composition at each position is almost the same.
Reproducible in taste . That is, it is close to the amount of both phosphorus and potassium compounds theoretically needed to obtain the stoichiometric ratio desired in the final catalyst composition in the aqueous solution used during coating (within ± 5%). It is possible to introduce only.
【００５７】加えて、本発明による方法の実施の簡単さ
は極めて顕著である。その配合の質は、活性相（被覆
層）が１５〜３３重量％に相当し、そして一般式：In addition, the simplicity of implementation of the method according to the invention is quite remarkable. The quality of the formulation corresponds to 15-33% by weight of active phase (coating layer) and the general formula:
【化５】 [Chemical 5]
【００５８】に相当する、被覆され、かつ特に活性な触
媒組成物を調製する場合に特に顕著な利点を構成する。
ただし、上記の式においてThis constitutes a particularly significant advantage when preparing coated and particularly active catalyst compositions which correspond to
However, in the above formula
【００５９】−Ａはコバルト、ニッケル、マンガン、マ
グネシウム及び／又は鉛、好ましくはコバルト及び／又
はニッケルの原子を表し、 −Ｂは砒素及び／又は硼素原子を表し、 −Ｃはカリウム以外のアルカリ金属原子及び／又はマグ
ネシウム以外のアルカリ金属土類金属原子を表し、 −ａは元素Ａの原子数の和を表し、２〜１２（２〜１２
を含む）であり；Ａがコバルト単独を表す場合、ａは８
〜１０（８〜１０を含む）であり、 −ｂは１０〜１２（１０〜１２を含む）であり、 −ｃは０〜２（０〜２を含む）であって、合計（ｂ＋
ｃ）は１２の値を有し、 −ｄは０．５〜４（０．５〜４を含む）であり、 −ｅは０．５〜４（０．５〜４を含む）であり、 −ｆ及びｇは各々０．００５〜０．０６（０．００５〜
０．０６を含む）、好ましくは０．０１〜０．０３
（０．０１〜０．０３を含む）であり、 −ｈは元素Ｂの原子数の和を表し、そして０〜４（０〜
４を含む）であり、 −ｉは元素Ｃの原子数の和を表し、そして０〜０．５
（０〜０．５を含む）であり、そして −ｘは他の諸成分の原子価を飽和するのに要する酸素の
原子数である。-A represents an atom of cobalt, nickel, manganese, magnesium and / or lead, preferably cobalt and / or nickel, -B represents an arsenic and / or boron atom, and -C represents an alkali metal other than potassium. Atom and / or an alkali metal earth metal atom other than magnesium, -a represents the sum of the number of atoms of the element A, 2 to 12 (2 to 12
When A represents cobalt alone, a is 8
-10 (including 8 to 10), -b is 10 to 12 (including 10 to 12), -c is 0 to 2 (including 0 to 2), and the total (b +
c) has a value of 12, -d is 0.5-4 (including 0.5-4), -e is 0.5-4 (including 0.5-4), -F and g are 0.005-0.06 (0.005-
0.06 included), preferably 0.01 to 0.03
(Including 0.01 to 0.03), -h represents the sum of the atomic numbers of the element B, and 0 to 4 (0 to
4), i represents the sum of the number of atoms of the element C, and 0 to 0.5.
(Including 0 to 0.5), and -x is the number of oxygen atoms required to saturate the valences of the other components.
【００６０】Ａはコバルト原子を表すのが好ましく、そ
して比ｆ／ｇは０．３〜３（０．３〜３を含む）、好ま
しくは０．５〜１．５（０．５〜１．５を含む）である
のが好ましい。A preferably represents a cobalt atom and the ratio f / g is 0.3 to 3 (including 0.3 to 3), preferably 0.5 to 1.5 (0.5 to 1. (Including 5) is preferable.
【００６１】低含量のドーパントＰ及びＫを有するこれ
らの触媒組成物はプロピレンの酸化によってアクロレイ
ンを製造する際に高い触媒活性と選択性とを同時にかつ
永続的に与える。These catalyst compositions with low contents of dopants P and K simultaneously and permanently give high catalytic activity and selectivity in the production of acrolein by the oxidation of propylene.
【００６２】[0062]
【実施例】次の実施例は本発明を例証するものである。The following example illustrates the invention.
【００６３】実施例１ （ａ）中間活性相の製造 ヘプタモリブデン酸アンモニウム８３．８ｋｇを７０〜
８０℃の温度に加熱することによって抵抗が１５０，０
００オーム・ｃｍより大きい脱イオン水３８０リットル
に溶解する。溶液を次に２０〜２５℃の温度に冷却す
る。ｐＨは５〜５．５である。 Example 1 (a) Preparation of intermediate active phase 70% of 83.8 kg of ammonium heptamolybdate was added.
Resistance to 150,0 by heating to a temperature of 80 ° C
Dissolve in 380 liters of deionized water greater than 00 ohm-cm. The solution is then cooled to a temperature of 20-25 ° C. The pH is 5 to 5.5.
【００６４】もう１つの反応容器に、同じ脱イオン水７
５リットルを入れ、８０℃に昇温する。次に、硝酸コバ
ルト６水和物１１５．１ｋｇ、水９分子を含有する硝酸
第二鉄１６．５ｋｇ、１００％硝酸２．２リットル、そ
して最後に硝酸ビスマス５水和物１９．２ｋｇを撹拌し
ながら導入する。完全に溶解させた後、温度を２０〜２
５℃に下げる。In another reaction vessel, the same deionized water 7
Add 5 liters and raise the temperature to 80 ° C. Next, 115.1 kg of cobalt nitrate hexahydrate, 16.5 kg of ferric nitrate containing 9 molecules of water, 2.2 liters of 100% nitric acid, and finally 19.2 kg of bismuth nitrate pentahydrate are stirred. While introducing. After completely dissolving, the temperature is 20 to 2
Lower to 5 ° C.
【００６５】上記金属硝酸塩類の溶液をヘプタモリブデ
ン酸塩の溶液に激しく撹拌しながら３０分かけて導入す
るとｐＨは１〜１．５に下がる。得られた懸濁液に次に
アンモニアを２００ｇ／Ｌ含有する溶液５．７５リット
ルを３０分かけて添加する。ｐＨは再び７に上がる。When the above solution of metal nitrates is introduced into the solution of heptamolybdate over 30 minutes with vigorous stirring, the pH drops to 1 to 1.5. 5.75 l of a solution containing 200 g / l of ammonia are then added to the suspension obtained over 30 minutes. The pH rises to 7 again.
【００６６】この媒体の温度を１時間かけて６０℃にも
たらし、撹拌しながらその温度に４時間保ち、次いで３
０分かけて約２２℃に下げる。The temperature of this medium is brought to 60 ° C. over 1 hour, kept at that temperature for 4 hours with stirring, then 3
Decrease to about 22 ° C over 0 minutes.
【００６７】この懸濁液を濾過し、次いで抵抗が１５
０，０００オーム・ｃｍより大きい脱イオン水５００リ
ットルで洗浄する。そのケーキを次にプレートに厚さ約
４〜５ｃｍで塗る。これらのプレートを１２０℃の電気
炉に２０時間入れて置く。The suspension is filtered and then with a resistance of 15
Rinse with 500 liters of deionized water greater than 10,000 ohm-cm. The cake is then spread on a plate with a thickness of about 4-5 cm. These plates are placed in an electric oven at 120 ° C. for 20 hours.
【００６８】電気炉を次に５時間かけて４００℃の温度
にもたらし、その温度を空気を循環させながら６時間保
持する。周囲温度までの冷却を５時間かけて行う。The electric furnace is then brought to a temperature of 400 ° C. over a period of 5 hours, which temperature is maintained for 6 hours while circulating air. Cool to ambient temperature over 5 hours.
【００６９】プレートの内容物をピン・ミルに入れて１
２５マイクロメーター未満の粒子寸法にする。かくし
て、中間活性相約１０２ｋｇが得られる。Put the contents of the plate into the pin mill and
Have a particle size of less than 25 micrometers. Approximately 102 kg of intermediate active phase are thus obtained.
【００７０】（ｂ）被覆を１５〜１８回転／分で回転
し、被覆操作開始時に、ダストが注意深く除かれた不活
性な支持体の球体としての、高温で焼結されたクレー球
体１２５ｋｇが入っている直径１．２５ｍのコーターの
中で行う。クレー球体はグルコース１００ｇ／リットル
の第一溶液で１０〜１２リットル／時の速度で噴霧する
ことによって前以て濡らされたものである。(B) The coating was spun at 15-18 rpm and at the start of the coating operation 125 kg of high temperature sintered clay spheres as inert support spheres were dedusted carefully. In a coater with a diameter of 1.25 m. The clay spheres were pre-wetted by spraying with a first solution of 100 g / l glucose at a rate of 10-12 l / h.
【００７１】球体が全て濡らされた時、シュートで粉末
状の中間活性相４４ｋｇを約５０分で導入する。粉末の
導入中にコーターを回転させ続け、そしてグルコースを
１００ｇ／Ｌ含有するほか燐酸二水素カリウムも５ｇ／
Ｌ含有する第二溶液をそれら球体に噴霧する。溶液の全
部、次いで中間活性相の全部が導入されたら、コーター
の回転を約数分間保持する。最後に、可撓性接続手段で
１００℃に加熱された空気を１．３〜１．５ｍ３／時で
供給して１５〜２０分かけてそれら球体を乾燥する。When all the spheres have been wetted, 44 kg of a powdery intermediate active phase are introduced in a chute in about 50 minutes. Continue to rotate the coater during the introduction of the powder and contain 100 g / L glucose and also 5 g / potassium dihydrogen phosphate.
A second solution containing L is sprayed on the spheres. Once all of the solution and then all of the intermediate active phase has been introduced, the coater spin is held for about a few minutes. Finally, the spheres are dried for 15 to 20 minutes by supplying air heated to 100 ° C. with a flexible connecting means at 1.3 to 1.5 m 3 / hour.
【００７２】こうして被覆、乾燥された球体を通風炉に
導入して最後の焼成を行う。これら通風炉の温度を６時
間かけて漸進的に２４０℃に、次いで８時間かけて４８
０℃にもたらす。４８０℃で６時間の第一段階が観察さ
れ、次いで１０時間かけて１５０℃に冷却したら、続い
て４８０℃に１０時間かけて戻す。４８０℃で６時間の
第二段階を行った後、最後に１０時間かけて周囲温度ま
で冷却する。The spheres thus coated and dried are introduced into a ventilation oven for final firing. The temperature of these ventilated furnaces was gradually increased to 240 ° C. over 6 hours and then 48 hours over 8 hours.
Bring to 0 ° C. A first stage of 6 hours at 480 ° C is observed, then cooled to 150 ° C over 10 hours, followed by a return to 480 ° C over 10 hours. After performing the second stage at 480 ° C. for 6 hours, finally cool to ambient temperature over 10 hours.
【００７３】次いで、通風炉から仕上げ触媒約１６９ｋ
ｇを取り出す。その触媒の２６％は式：Next, from the ventilation furnace, about 169 k of finished catalyst
Take out g. 26% of the catalyst has the formula:
【化６】 [Chemical 6]
【００７４】に相当する活性相から構成されている。It consists of an active phase corresponding to
【００７５】比較例Ａ 実施例１に示される操作条件下で操作を行って調製した
焼成中間活性相１００ｋｇを燐酸二水素カリウム２７０
ｇを含有する水性溶液４リットルとミキサー中で混合す
る。この混合で全体の粘度が相当に低下されるので、混
合は困難であることが証明された。次に、約１５分後に
全体を炉の中で１２０℃において１５時間乾燥する。COMPARATIVE EXAMPLE A 100 kg of the calcined intermediate active phase, prepared by operating under the operating conditions given in Example 1, were treated with potassium dihydrogen phosphate 270.
Mix in an mixer with 4 liters of an aqueous solution containing g. Mixing proved difficult because the overall viscosity was significantly reduced with this mixing. Then, after about 15 minutes, the whole is dried in an oven at 120 ° C. for 15 hours.
【００７６】こうしてドープされた活性相４４ｋｇを次
に、燐酸二水素カリウムを第二被覆溶液に用いないこと
を除いては同じ操作を行って被覆する。44 kg of the thus doped active phase are then coated by the same procedure except that potassium dihydrogen phosphate is not used in the second coating solution.
【００７７】乾燥及び焼成は実施例１に記載のものと同
じである。Drying and baking are the same as those described in Example 1.
【００７８】比較例Ｂ 被覆溶液に燐酸二水素カリウムを導入しない点を除いて
実施例１の条件と同じ条件下でもう１つの触媒を製造す
る。 Comparative Example B Another catalyst is prepared under the same conditions as in Example 1 except that potassium dihydrogen phosphate is not introduced into the coating solution.
【００７９】実施例２ ドーパントの活性相の層中への配合と分布 仕上げ触媒へのドーパントの配合率と分布量を知るため
には触媒活性相の層厚中の燐元素及びカリウム元素を定
量することが必要である。まず、活性相の層の色々なフ
ラクションの機械的磨砕による物理的分離を行う。 Example 2 Blending and Distribution of Dopant in Active Layer in Layer In order to know the blending ratio and the amount of distribution of dopant in the finishing catalyst, the phosphorus element and the potassium element in the layer thickness of the catalyst active phase were quantified. It is necessary. First, the physical separation of the various fractions of the active phase layer is carried out by mechanical milling.
【００８０】この機械的磨砕のために、仕上げ触媒３０
ｇを容積５０ｍＬの密閉金属容器に入れる。この全体を
振幅約４ｃｍの垂直振動を１分当たり７００回行う装置
に入れる。For this mechanical grinding, the finishing catalyst 30
g in a closed metal container with a volume of 50 mL. The whole is put into a device that carries out vertical vibration with an amplitude of about 4 cm 700 times per minute.
【００８１】１０分の終点で装置を止め、その容器を開
ける。磨砕によって分離した活性相のダストをふるいに
かけて触媒の球体を分離する。このダストを集め、秤量
し、次いで溶解してドーパントを定量する。燐をプラズ
マ発光分光分析で、またカリウムを発炎分光分析で定量
する。At the end of 10 minutes the device is stopped and the container is opened. The active phase dust separated by grinding is sieved to separate the catalyst spheres. The dust is collected, weighed, and then dissolved to quantify the dopant. Phosphorus is quantified by plasma emission spectroscopy and potassium by flame emission spectroscopy.
【００８２】次に、球体を上記容器に再び入れ、磨砕を
更に１０分間行う。活性相の新しいフラクションを集
め、次いで定量する。この操作を磨砕に付された触媒に
それ以上実質的に活性相が視認できなくなり、触媒が小
さくなって実質的にそれらの中央の不活性球体になって
しまうまで２回以上再現する。Next, the spheres are placed again in the container and milled for another 10 minutes. A new fraction of the active phase is collected and then quantified. This operation is repeated twice or more until the milled catalyst becomes substantially invisible of the active phase anymore and the catalyst becomes smaller and becomes essentially the central inert spheres thereof.
【００８３】各採集物から、磨砕が完全に漸進的に起き
ていると仮定して、採集された活性相のフラクションが
位置した場所を見積もることが可能である。即ち、第一
採集物だけが層の最も外側の粒子に対応し、最後の採集
物だけが層の最も内側の粒子に対応する。この仮説−こ
れは真実に十分に近いものである−は磨砕によってはぎ
取られた活性相のフラクションが位置した場所の相対的
位置範囲（厚さの％で）を決めるのを可能にする。From each collection, it is possible to estimate where the fraction of active phase collected is located, assuming that the milling is completely progressive. That is, only the first collection corresponds to the outermost particles of the layer and only the last collection corresponds to the innermost particles of the layer. This hypothesis-which is close enough to the truth-allows to determine the relative positional range (in% of thickness) of where the fraction of the active phase which has been stripped by milling is located.
【００８４】支持体を形成している球体が粗面となって
いる故に、集められたダストの部分はこれら球体の構成
物質、即ちクレー以外の何物でもない。集められたダス
ト中のクレーのこの割合は磨砕時間が増すにつれて重要
さが増し、従ってそれは最後の採集物においてより重要
である。従って、支持体のクレー中に含有されるカリウ
ムの量を定量可能とするために、高温で焼結されたクレ
ーのこれら不活性球体の試料を粉砕した。他方で、集め
られたダストをＸ−線蛍光分析法で分析してそれらダス
トが含有するクレーの割合を機械的に標準化された混合
物に対する珪素元素の応答により求める。あらゆること
を考慮に入れた上で、各採集物中に含有されるカリウム
と燐の量を差として求めることがかくして可能である。Due to the rough surface of the spheres forming the support, the collected dust fraction is nothing more than a constituent of these spheres, namely clay. This proportion of clay in the collected dust becomes more important as the milling time increases, so it is more important in the final harvest. Therefore, in order to be able to quantify the amount of potassium contained in the clay of the support, a sample of these inert spheres of clay sintered at high temperature was ground. On the other hand, the collected dusts are analyzed by X-ray fluorescence spectrometry to determine the proportion of clay they contain by the response of elemental silicon to a mechanically standardized mixture. Taking everything into account, it is thus possible to determine the amount of potassium and phosphorus contained in each collection as a difference.
【００８５】実施例１の触媒について得られた値をドー
パントの分布が完全に均一である場合に期待される理論
値と比較して以下の表１に示す：The values obtained for the catalyst of Example 1 are compared in table 1 below with the theoretical values expected when the distribution of the dopant is perfectly uniform:
【表１】 [Table 1]
【００８６】かくして、ドーパントの含量は全体として
分布が理想的に均一であった場合に期待される値に非常
に近いことは明らかである。（燐についての持続的な違
いは多分測定の系統的な測定誤差か、又は支持体のクレ
ーの僅かな損失で説明される。）全休として、活性相中
のフラクション中の含量と期待理論含量がほぼ一致して
おり、配合率はコントロール可能で、Ｋ又はＰの含量が
位置による相違がなくほぼあらゆる位置（中央クレーを
除く）で一致しているという意味で、１００％に近い再
現性を有する。尚、表１において、位置（厚さの％）
が、表の下部にいくに従い（「外側１００〜２６」から
「中央クレー」に進むに従い）、機械的磨砕の回数が増
加していく。 又、「粗含量」とは、各位置（各機械的磨
砕のサイクル）ごとに集められたフラクション中のＫ，
Ｐ，あるいはクレーの測定値を意味する。 又、「活性相
のフラクション中の含量」とは、各位置におけるフラク
ションからクレー重量を除いた「活性相」の中のＫ又は
Ｐの含量を示し、次式、 （Ｋ又はＰの粗含量（ｐｐ
ｍ））−（クレーの粗含量（％）×１０ −２ ）× （中央
クレーに含まれるＫ又はＰの粗含量（ｐｐｍ））で表わ
される。 「期待理論含量」とは、次式、（活性相の化学
式におけるＫ又はＰの化学量論計数）×（Ｋ又はＰの原
子量）／（活性相の分子量）で表わされる。たとえば、
Ｋの期待理論含量を求めようとすると、実施例１に記載
の It is thus clear that the content of dopants is very close to the value that would be expected if the overall distribution were ideally uniform. (Persistent differences of phosphorus is described probably systematic or measurement errors of measurement, or a slight loss of clay support.) As Zenkyu, active phase
The expected theoretical content of the fractions of
Cage, blending rate control possible, the content of K or P
There is no difference in position and almost any position (center clay
In the sense that is consistent with the exception), again close to 100%
It has reality . In Table 1, the position (% of thickness)
But as you go to the bottom of the table (from "outside 100-26"
The number of mechanical grinding increases as you go to "Central Clay"
To add. Also, "coarse content" means each position (each mechanical polishing
K in the fractions collected for each crushing cycle,
P, or the measured value of clay. In addition, "active phase
The content in the fraction of the
K in the "active phase" excluding the clay weight from the
The content of P is shown by the following formula: (K or P crude content (pp
m))-(crude content of clay (%) × 10 −2 ) × (center
Expressed by the crude content (ppm) of K or P contained in clay
To be done. The "expected theoretical content" is defined by
Stoichiometric count of K or P in the formula) x (source of K or P)
Molecular weight) / (molecular weight of active phase). For example,
When seeking the expected theoretical content of K, it is described in Example 1.
of
【化６】に相当する活性相のＫの化学理論係数が０．０The chemical theory coefficient of K of the active phase corresponding to
２８であり、該活性相の分子量は２７９１であるので、28 and the molecular weight of the active phase is 2791,
０．０２８×３９．１／２７９１＝３９２ｐｐｍとな0.028 × 39.1 / 2791 = 392 ppm
る。It
【００８７】活性相の厚さにおける分布に関して、それ
らの含量はカリウムについては最内層の値を除けば±１
５％で一定のようである。最内層の値はその殆どがクレ
ーの存在によって影響されている可能性がある。燐につ
いては±３０％の変化が認められ、明らかに層の深さの
関数としてより一層系統的である。Regarding the distribution in the thickness of the active phase, their contents are ± 1 for potassium except the value of the innermost layer.
Seems to be constant at 5%. Most of the values in the innermost layer may be affected by the presence of clay. A change of ± 30% was observed for phosphorus, clearly more systematic as a function of layer depth.
【００８８】比較のために、比較例Ａに従って調製した
触媒について測定した値を以下の表２に示す：For comparison, the values measured for the catalyst prepared according to Comparative Example A are shown in Table 2 below:
【表２】 [Table 2]
【００８９】かくして、これらの値はドーパントの分布
が均一であるとすれば期待される値とは完全に異なるこ
とが明らかに認められる。試験されたドープ済み活性相
のバッチのフラクションはドーパントに富み過ぎること
を、即ちカリウムについては４倍以上、燐においては２
倍以上であることを証明している。あらゆる可能性にお
いて、これは混合によって引き起こされた分布の不均一
さに起因する。ドーパントの配合率はコントロール可能
とは思われない。It is thus clearly seen that these values are completely different from what would be expected if the dopant distribution were uniform. The fraction of batches of doped active phase tested was too rich in dopant, ie more than 4 times for potassium and 2 for phosphorus.
Prove that it is more than double. In all possibilities this is due to the non-uniformity of the distribution caused by mixing. Dopant loadings do not seem to be controllable.
【００９０】実施例３ 仕上げ触媒の機械的耐性に対するドーパントの影響 仕上げ触媒の機械的耐性は磨砕試験によって測定され
る。磨砕試験は次の通りである。 Example 3 Effect of Dopants on Mechanical Resistance of Finished Catalysts Mechanical resistance of finished catalysts is measured by a grinding test. The grinding test is as follows.
【００９１】仕上げ触媒１００ｇを、１０回転／分で回
転しているモーターの水平シャフトに固定された外径２
２０ｍｍ、幅４０ｍｍのプレキシガラス（ＰｌｅＸｉｇ
ｌａｓｓ：登録商標）製ドラムに導入する。ドラムの内
部には長さ４５ｍｍ、幅４０ｍｍの、６枚の平らなプレ
キシガラス製のブレードが等間隔でそれらの固定基礎を
通る直径に対して４０゜傾斜して固定されている。100 g of the finished catalyst was fixed on the horizontal shaft of a motor rotating at 10 rpm to obtain an outer diameter of 2
20mm, 40mm width Plexiglas (PleXig
lass (registered trademark). Inside the drum, six flat Plexiglas blades 45 mm long and 40 mm wide are fixed at equal intervals at an angle of 40 ° with respect to the diameter passing through their fixed bases.
【００９２】ドラムの回転方向は、ドラムの接線速度の
ベクトルをブレードの任意の１枚の固定点で表す場合
に、これがブレードと５０°の角度をなすような方向で
ある。The direction of rotation of the drum is such that when the vector of the tangential velocity of the drum is represented by any one fixed point on the blade, this makes an angle of 50 ° with the blade.
【００９３】球体をドラムから取り出し、ふるいにかけ
て微粉物を分離した後秤量する。このようにして測定し
た質量をｍ５とする。装置からダストを除去し、次いで
それら球体を再導入する。１０分の終点で新しく秤量を
行い、質量ｍ１５を得る。The spheres are taken out of the drum, sieved to separate fines, and then weighed. The mass measured in this way is m 5 . Remove dust from the device and then reintroduce the spheres. A new weighing is carried out at the end of 10 minutes to obtain the mass m 15 .
【００９４】磨砕率は磨砕装置によって除去された活性
相の割合と定義される。活性相の量Ｔに関してそれを次
のようにして計算する：The milling rate is defined as the proportion of active phase removed by the milling device. It is calculated in terms of the amount T of active phases as follows:
【００９５】５分後の磨砕率（％）の値は（１００−ｍ
５）×１００／Ｔである。The value of the grinding rate (%) after 5 minutes was (100-m
5 ) × 100 / T.
【００９６】合計磨砕時間１５分後の磨砕率（％）の値
は（１００−ｍ１５）×１００／Ｔである。The value of the grinding rate (%) after 15 minutes of the total grinding time is (100-m 15 ) × 100 / T.
【００９７】本発明の方法に従って実施例１の条件によ
り製造した触媒１６９ｋｇの色々なバッチに対して行っ
た磨砕の測定結果を比較例Ｂの条件により製造した、従
ってドープされていない触媒に対して行った測定結果に
比較して次表に示す。Catalysts prepared according to the method of the invention according to the conditions of Example 1 The results of the grinding measurements carried out on different batches of 169 kg are compared with the catalyst prepared according to the conditions of Comparative Example B, and thus the undoped catalyst. The results are shown in the following table in comparison with the measurement results.
【表３】 [Table 3]
【００９８】触媒はこれらの測定結果が磨砕１分当たり
１％未満である場合にその瞬間から固体と考えられるの
で、本発明の方法に従って製造された触媒は非常に耐性
であることは明らかである。加えて、異なるバッチにお
ける結果の明白な分散には、これらの値は全て非常に小
さいので何んらの重要な意味もない。It is clear that the catalyst prepared according to the process of the invention is very resistant, since the catalyst is considered to be solid from that moment on when these measured results are less than 1% per minute of grinding. is there. In addition, the apparent variance of results in different batches is of no significance because all these values are very small.
【００９９】期待され得ただろうものに反して，被覆溶
液におけるドーパントの存在は触媒の機械的耐性を有意
に変成しないことは明らかである。Contrary to what might have been expected, it is clear that the presence of the dopant in the coating solution does not significantly alter the mechanical resistance of the catalyst.
【０１００】実施例４ 本発明に従って調製した配合物の活性 実施例１に従って製造した触媒試料１００ｍＬをプロピ
レンのアクロレインへの酸化反応において試験する。使
用反応容器は内径２１ｍｍ、高さ５０ｃｍのものであ
る。 Example 4 Activity of Formulations Prepared According to the Invention A 100 mL catalyst sample prepared according to Example 1 is tested in the oxidation reaction of propylene to acrolein. The reaction vessel used has an inner diameter of 21 mm and a height of 50 cm.
【０１０１】砂浴により加熱されたこの反応容器に導入
した反応混合物には容量％で７％のプロピレン、５７％
の空気及び３６％の水蒸気が含まれている。プロピレン
の供給を触媒１リットル当たりプロピレン約２５０ｇ／
時の仕込み量が達成されるように調整する。反応容器の
出口圧力を１．８バール絶対圧に調整する。The reaction mixture introduced into this reaction vessel heated by a sand bath contains 7% by volume of propylene, 57%
Of air and 36% water vapor. About 250 g of propylene per liter of catalyst /
Adjust to achieve the hourly charge. The outlet pressure of the reaction vessel is adjusted to 1.8 bar absolute pressure.
【０１０２】反応容器からの流出物には窒素、酸素、水
蒸気、プロピレン、アクロレイン、アクリル酸、酢酸、
アセトアルデヒド、一酸化炭素及び二酸化炭素、その他
少量の不純物のガス状混合物が含まれている。各生成物
の割合は気層クロマトグラフにより測定することが可能
であり、かくして触媒性能は次式により計算される。即
ち、The effluent from the reaction vessel contains nitrogen, oxygen, steam, propylene, acrolein, acrylic acid, acetic acid,
It contains a gaseous mixture of acetaldehyde, carbon monoxide and carbon dioxide, and other minor impurities. The proportion of each product can be measured by gas phase chromatography and thus the catalyst performance is calculated by the following equation. That is,
【０１０３】転化率は、これをＸｇと書くと、The conversion rate is expressed as Xg,
【式１】 [Formula 1]
【０１０４】である。また、生成物ｉについての選択率
は、これをＳｉと書くと、It is Also, the selectivity for the product i is written as Si,
【式２】 [Formula 2]
【０１０５】であり、そのＲｉは生成物ｉの収率であ
る。収率は転化率Ｘｇに生成物ｉについての選択率を乗
じた積、即ちＲｉ＝Ｘｇ×Ｓｉである。Where Ri is the yield of product i. The yield is the product of conversion Xg times the selectivity for product i, ie Ri = Xg × Si.
【０１０６】実施例１に従って製造した触媒について、
得られた結果を次表に示す。For the catalyst prepared according to Example 1,
The obtained results are shown in the following table.
【表４】 [Table 4]
【０１０７】これらの結果は、かくして本発明による方
法に従って製造された触媒は良好な触媒性能、即ちプロ
ピレンの高転化率値においてアクロレインの高収率を達
成できるようにすることを明らかに示している。These results clearly show that the catalyst thus produced according to the process according to the invention allows to achieve good catalytic performance, ie a high yield of acrolein at high conversion values of propylene. .
Claims (10)
れを焼成し、続いて該焼成組成物を粉砕し、外表面が粗
になっている不活性な固体支持体の粒子を該粉砕組成物
又はそれを含有する混合物により被覆し、続いてそのよ
うに被覆された粒子を焼成する工程を含んで成る、プロ
ピレンからアクロレインを合成するための、特に燐及び
カリウムでドープされたビスマスタイプ及び鉄タイプの
両モリブデン酸塩の被覆触媒の製造法において、 （ａ）触媒的に活性な該中間組成物はカリウム及び燐を
含まず、そして （ｂ）該カリウムと該燐の導入を被覆段階中に実施する
ことを特徴とする前記方法。1. A catalytically active intermediate composition is prepared, which is calcined and subsequently the calcined composition is ground to obtain particles of an inert solid support having a roughened outer surface. coated with the pulverized composition or mixture containing it, followed by comprising a step of firing such coated particles, pro
In a process for the preparation of acrolein from pyrene, in particular a coated catalyst of both bismuth-type and iron-type molybdates doped with phosphorus and potassium, (a) the catalytically active intermediate composition comprises potassium and A process as described above, characterized in that it is phosphorus-free and (b) the introduction of the potassium and the phosphorus is carried out during the coating step.
化合物及び少なくとも１種の燐化合物の水性溶液を導入
することを特徴とする請求項１に記載の触媒の製造法。2. A process according to claim 1, wherein an aqueous solution of at least one potassium compound and at least one phosphorus compound is introduced during the coating step.
度が２５℃において測定して１０ｇ／Ｌ以上であること
を特徴とする請求項２に記載の方法。3. The method according to claim 2, wherein the solubility of the phosphorus compound and the potassium compound in water measured at 25 ° C. is 10 g / L or more.
は２種以上のカリウム化合物の添加後の水性溶液のｐＨ
が３〜１１であることを特徴とする請求項２又は３に記
載の方法。4. The pH of the aqueous solution after the addition of one or more phosphorus compounds and one or more potassium compounds.
Is 3-11, The method of Claim 2 or 3 characterized by the above-mentioned.
特徴とする請求項２〜４のいずれか１項に記載の方法。5. The method according to claim 2, wherein the aqueous solution contains an adhesive.
とを特徴とする請求項１〜５のいずれか１項に記載の方
法。6. The method according to claim 1, wherein the potassium is introduced in the form of a potash.
酸塩の形で導入することを特徴とする請求項１〜６のい
ずれか１項に記載の方法。7. The method according to claim 1, wherein phosphorus is introduced in the form of phosphoric acid or a mineral or organic phosphate.
水素カリウム又は燐酸二水素カリウムの形で導入するこ
とを特徴とする請求項１〜７のいずれか１項に記載の方
法。8. A part or all of phosphorus and potassium is phosphoric acid-
8. Method according to any one of claims 1 to 7, characterized in that it is introduced in the form of potassium hydrogen or potassium dihydrogen phosphate.
び燐化合物の量が最終触媒組成物に対して所望とされる
化学量論比を得るのに理論的に必要なカリウム及び燐の
量に対して±５％以内に相当する量であることを特徴と
する請求項１〜８のいずれか１項に記載の方法。9. The amount of potassium and phosphorus compounds introduced into the aqueous solution is based on the amount of potassium and phosphorus theoretically required to obtain the desired stoichiometric ratio for the final catalyst composition. 9. The method according to claim 1, wherein the amount is within ± 5%.
温度で実施することを特徴とする請求項１〜９のいずれ
か１項に記載の方法。10. The method according to claim 1, wherein the baking of the coated particles is carried out at a temperature of 450 to 500 ° C.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR9016389A FR2670685B1 (en) | 1990-12-20 | 1990-12-20 | PROCESS FOR THE PREPARATION OF COATED CATALYSTS BASED ON BISMUTH AND IRON MOLYBDATES DOPED WITH PHOSPHORUS AND POTASSIUM. |
| FR9016389 | 1990-12-20 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04300649A JPH04300649A (en) | 1992-10-23 |
| JPH0763630B2 true JPH0763630B2 (en) | 1995-07-12 |
Family
ID=9403763
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3361144A Expired - Lifetime JPH0763630B2 (en) | 1990-12-20 | 1991-12-20 | Process for the preparation of coated catalysts based on both bismuth and iron molybdates doped with phosphorus and potassium |
Country Status (9)
| Country | Link |
|---|---|
| US (1) | US5221653A (en) |
| EP (1) | EP0493275B1 (en) |
| JP (1) | JPH0763630B2 (en) |
| CN (1) | CN1032461C (en) |
| BR (1) | BR9105533A (en) |
| CA (1) | CA2058073C (en) |
| DE (1) | DE69105709T2 (en) |
| ES (1) | ES2064969T3 (en) |
| FR (1) | FR2670685B1 (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2718061B1 (en) * | 1994-04-01 | 1996-04-26 | Rhone Poulenc Chimie | Catalyst compositions of the coated type, comprising nickel, cobalt, molybdenum and their use for the preparation of unsaturated aldehydes. |
| JP3793317B2 (en) * | 1996-05-14 | 2006-07-05 | 日本化薬株式会社 | Catalyst and method for producing unsaturated aldehyde and unsaturated acid |
| DE19855913A1 (en) * | 1998-12-03 | 2000-06-08 | Basf Ag | Multimetal oxide mass for the gas-phase catalytic oxidation of organic compounds |
| US20060088447A1 (en) * | 2002-05-28 | 2006-04-27 | Pss Bio Instruments | Specimen distributing device, coating part manufacturing method, specimen distributing method and substrate activating device |
| GB0413605D0 (en) * | 2004-06-17 | 2004-07-21 | Addex Pharmaceuticals Sa | Novel compounds |
| US7649112B2 (en) | 2005-07-25 | 2010-01-19 | Saudi Basic Industries Corporation | Integrated plant for producing 2-ethyl-hexanol and methacrylic acid and a method based thereon |
| US7649111B2 (en) | 2005-07-25 | 2010-01-19 | Saudi Basic Industries Corporation | Catalyst for the oxidation of a mixed aldehyde feedstock to methacrylic acid and methods for making and using same |
| US7851397B2 (en) | 2005-07-25 | 2010-12-14 | Saudi Basic Industries Corporation | Catalyst for methacrolein oxidation and method for making and using same |
| US7732367B2 (en) | 2005-07-25 | 2010-06-08 | Saudi Basic Industries Corporation | Catalyst for methacrolein oxidation and method for making and using same |
| KR100932373B1 (en) * | 2007-05-30 | 2009-12-16 | 에스케이에너지 주식회사 | Method for preparing multicomponent bismuth molybdate catalyst according to pH change and method for preparing 1,3-butadiene using the catalyst |
| US20090056994A1 (en) * | 2007-08-31 | 2009-03-05 | Kuhr Werner G | Methods of Treating a Surface to Promote Metal Plating and Devices Formed |
| US8921257B2 (en) | 2011-12-02 | 2014-12-30 | Saudi Basic Industries Corporation | Dual function partial oxidation catalyst for propane to acrylic acid conversion |
| US8722940B2 (en) | 2012-03-01 | 2014-05-13 | Saudi Basic Industries Corporation | High molybdenum mixed metal oxide catalysts for the production of unsaturated aldehydes from olefins |
Family Cites Families (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4077912A (en) * | 1972-10-12 | 1978-03-07 | Standard Oil Company | Catalysts useful for exothermic reactions |
| US4040978A (en) * | 1975-11-28 | 1977-08-09 | Monsanto Company | Production of (amm)oxidation catalyst |
| FR2364061A1 (en) * | 1976-09-14 | 1978-04-07 | Rhone Poulenc Ind | NEW CATALYST FOR THE PREPARATION OF UNSATURATED A-B ALDEHYDES BY OXIDATION OF OLEFINS IN GAS PHASE AND ITS PREPARATION PROCESS |
| US4148757A (en) * | 1977-08-10 | 1979-04-10 | The Standard Oil Company | Process for forming multi-component oxide complex catalysts |
| US4267386A (en) * | 1978-11-13 | 1981-05-12 | Celanese Corporation | Olefin oxidation catalyst |
| DE2909597A1 (en) * | 1979-03-12 | 1980-09-25 | Basf Ag | METHOD FOR THE PRODUCTION OF 3 TO 4 C-ATOMES CONTAINING ALPHA, BETA -OLEFINICALLY UNSATURATED ALDEHYDES |
| US4332971A (en) * | 1979-08-09 | 1982-06-01 | Celanese Corporation | Process for the oxidation of olefinically unsaturated hydrocarbons to aldehydes using attrition resistant catalysts |
| FR2481146A1 (en) * | 1980-04-25 | 1981-10-30 | Rhone Poulenc Ind | PROCESS FOR THE PREPARATION OF CATALYSTS BASED ON OXIDES OF MOLYBDENUM AND / OR TUNGSTEN AND OXIDES OF OTHER METALS |
| US4414134A (en) * | 1981-01-05 | 1983-11-08 | The Standard Oil Co. | Impregnating catalysts |
| DE3125062C2 (en) * | 1981-06-26 | 1984-11-22 | Degussa Ag, 6000 Frankfurt | Process for the production of abrasion-resistant coated catalysts and the use of a catalyst obtained in this way |
| JPS5872550A (en) * | 1981-10-26 | 1983-04-30 | Asahi Chem Ind Co Ltd | Preparation of methacrylonitrile |
| JPS58119346A (en) * | 1982-01-06 | 1983-07-15 | Nippon Shokubai Kagaku Kogyo Co Ltd | Catalyst for oxidizing propylene |
| US4710484A (en) * | 1982-06-25 | 1987-12-01 | The Standard Oil Company | Method for preparing a supported mixed-metal oxide oxidation catalyst |
| US4537874A (en) * | 1982-10-22 | 1985-08-27 | Nippon Shokubai Kagaku Kogyo Co Ltd | Catalyst for production of unsaturated aldehydes |
| JPS6126419A (en) * | 1984-07-17 | 1986-02-05 | 三菱電機株式会社 | Breaker controller |
| DE3827639A1 (en) * | 1988-08-16 | 1990-02-22 | Basf Ag | CATALYST FOR THE OXIDATION AND AMMONOXIDATION OF (ALPHA), SS-UNSATURATED HYDROCARBONS |
| DE3930533C1 (en) * | 1989-09-13 | 1991-05-08 | Degussa Ag, 6000 Frankfurt, De |
-
1990
- 1990-12-20 FR FR9016389A patent/FR2670685B1/en not_active Expired - Fee Related
-
1991
- 1991-12-16 DE DE69105709T patent/DE69105709T2/en not_active Expired - Fee Related
- 1991-12-16 EP EP91420454A patent/EP0493275B1/en not_active Expired - Lifetime
- 1991-12-16 ES ES91420454T patent/ES2064969T3/en not_active Expired - Lifetime
- 1991-12-19 CA CA002058073A patent/CA2058073C/en not_active Expired - Fee Related
- 1991-12-19 BR BR919105533A patent/BR9105533A/en not_active IP Right Cessation
- 1991-12-20 JP JP3361144A patent/JPH0763630B2/en not_active Expired - Lifetime
- 1991-12-20 CN CN91111733.4A patent/CN1032461C/en not_active Expired - Fee Related
- 1991-12-20 US US07/811,127 patent/US5221653A/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| ES2064969T3 (en) | 1995-02-01 |
| CN1032461C (en) | 1996-08-07 |
| DE69105709D1 (en) | 1995-01-19 |
| CA2058073A1 (en) | 1992-06-21 |
| FR2670685B1 (en) | 1995-03-10 |
| EP0493275A1 (en) | 1992-07-01 |
| DE69105709T2 (en) | 1995-07-20 |
| JPH04300649A (en) | 1992-10-23 |
| CA2058073C (en) | 1996-06-18 |
| BR9105533A (en) | 1992-09-01 |
| CN1062676A (en) | 1992-07-15 |
| EP0493275B1 (en) | 1994-12-07 |
| US5221653A (en) | 1993-06-22 |
| FR2670685A1 (en) | 1992-06-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3786297B2 (en) | Catalyst production method | |
| JP2603776B2 (en) | Catalyst composition for production of α, β-unsaturated aldehyde by oxidation of olefin | |
| KR100362159B1 (en) | Manufacturing method of supported catalyst for methacrolein and methacrylate synthesis | |
| JPH0763630B2 (en) | Process for the preparation of coated catalysts based on both bismuth and iron molybdates doped with phosphorus and potassium | |
| JP4247565B2 (en) | Catalyst for producing acrylic acid and method for producing acrylic acid using the same | |
| JP4788040B2 (en) | Vanadium / phosphorus mixed oxide catalyst precursor | |
| US4024074A (en) | Catalyst for the oxidation of methanol to formaldehyde and process for preparing the same | |
| JPS61209906A (en) | Heteropoly acid h8pmo10v039, anhydride thereof pm010v035, these manufacture, catalyst for manufacturing organic compound and manufacture of methacrylic acid | |
| JP5210834B2 (en) | Method for producing catalyst for acrylonitrile synthesis and method for producing acrylonitrile | |
| JP6653871B2 (en) | Catalyst for producing methacrylic acid, method for producing the same, and method for producing methacrylic acid | |
| JP2520282B2 (en) | Method for producing acrylonitrile | |
| JPH0596B2 (en) | ||
| JPH11343262A (en) | Production of acrylic acid | |
| JP5210835B2 (en) | Method for producing catalyst for acrylonitrile synthesis and method for producing acrylonitrile | |
| JP2004008834A (en) | Method for producing catalyst for use in manufacturing methacrylic acid | |
| JP3342794B2 (en) | Method for producing supported catalyst for synthesis of methacrolein and methacrylic acid | |
| JPS582232B2 (en) | Method for producing acrylonitrile | |
| JPS63315147A (en) | Catalyst for synthesis of methacrolein and preparation thereof showing excellent reproducibility | |
| JP4425743B2 (en) | Method for producing fluidized bed catalyst for acrylonitrile synthesis | |
| JP5011177B2 (en) | Method for producing catalyst for acrylonitrile synthesis and method for producing acrylonitrile | |
| JPWO2018016155A1 (en) | Method for producing metal oxide catalyst | |
| JP7188707B2 (en) | Catalyst for producing methacrylic acid, method for producing the same, and method for producing methacrylic acid and methacrylic acid ester | |
| JP2004141823A (en) | Manufacturing method of catalyst for production of methacrylic acid and manufacturing method of methacrylic acid | |
| JP2000246108A (en) | Metal oxide catalyst and production of acrylic acid using same | |
| KR20210080087A (en) | Manufacturing method of ammoxidation catalyst for propylene, and ammoxidation methode using the same catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 19960305 |